CN111969098A - High-absorption thermopile and manufacturing method thereof - Google Patents

High-absorption thermopile and manufacturing method thereof Download PDF

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Publication number
CN111969098A
CN111969098A CN202010874367.1A CN202010874367A CN111969098A CN 111969098 A CN111969098 A CN 111969098A CN 202010874367 A CN202010874367 A CN 202010874367A CN 111969098 A CN111969098 A CN 111969098A
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CN
China
Prior art keywords
thermopile
nano
layer
infrared absorption
infrared
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CN202010874367.1A
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Chinese (zh)
Inventor
周娜
毛海央
李俊杰
高建峰
杨涛
李俊峰
王文武
陈大鹏
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Institute of Microelectronics of CAS
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Institute of Microelectronics of CAS
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Priority to CN202010874367.1A priority Critical patent/CN111969098A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/10Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
    • G01J5/12Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using thermoelectric elements, e.g. thermocouples
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01Manufacture or treatment
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N19/00Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
    • H10N19/101Multiple thermocouples connected in a cascade arrangement

Abstract

A high absorption thermopile and its preparation method, the said thermopile includes the infrared absorption layer; wherein, the infrared absorption layer comprises a spin-on carbon material. According to the invention, the spin-coating carbon material is applied to the thermopile for the first time to serve as the infrared absorption layer material, and the spin-coating carbon material is utilized to enhance the light absorption effect of the infrared absorption layer and improve the infrared absorption performance of the thermopile.

Description

High-absorption thermopile and manufacturing method thereof
Technical Field
The invention relates to the technical field of infrared detectors, in particular to a high-absorption thermopile and a manufacturing method thereof.
Background
Currently, infrared detectors are widely used in the civil and military fields, and thermopile infrared detectors are the earliest developed one of many types of infrared detectors. The optical fiber has the advantages of capability of working at normal temperature, wide response wave band, low manufacturing cost and the like, so the optical fiber is developed very quickly and is very widely applied. In the process preparation of the thermopile infrared detector, the compatibility of the manufacturing process and the integrated circuit process is a main method for forming a large-scale detection array, improving the detection response rate and reducing the process manufacturing cost.
In the manufacturing process of the thermopile, the design of the absorption layer is very critical, and the two aspects of the structure design and the material selection are mainly embodied. On the one hand, a large absorption rate for infrared radiation is required, and on the other hand, the fabrication process thereof is required to be compatible with a CMOS (complementary metal oxide semiconductor) process. Currently, most studied infrared absorption layer materials mainly include "black" substances (gold black, silver black, etc.), silicides (SiN, SiC, etc.), etc., and they have the following characteristics: the absorption rate of the metal black to infrared radiation is high, but the manufacturing process of the metal black is complex and is not compatible with CMOS; the silicon-based composite film (SiN, SiC, etc.) has a certain absorption of light in a longer wavelength range, but the light absorption efficiency is lower than that of metal black.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a high absorption thermopile and a manufacturing method thereof, which are intended to at least partially solve at least one of the above mentioned technical problems.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
as an aspect of the present invention, there is provided a thermopile including an infrared absorbing layer;
wherein, the infrared absorption layer comprises a spin-on carbon material.
As another aspect of the present invention, there is also provided a method of manufacturing a thermopile, including: an infrared absorbing layer including a spin-on carbon material is formed by a spin-on method.
Based on the technical scheme, compared with the prior art, the invention has at least one or one part of the following beneficial effects:
(1) according to the invention, the spin-coating carbon material is applied to the infrared absorption layer of the thermopile for the first time, and the spin-coating carbon material is utilized to enhance the light absorption effect of the infrared absorption layer and improve the infrared absorption performance of the thermopile;
(2) the invention combines a material (used as a middle infrared absorption layer) compatible with CMOS (complementary metal oxide semiconductor) and spin-on carbon (SOC used as an anti-reflection layer and a near infrared absorption layer) to form a composite laminated light absorption structure, thereby realizing the effect of supplementing and absorbing light of different wave bands;
(3) according to the invention, a nano-column, a nano-wire or a nano-cone structure of SOC is formed by photoetching and etching technologies, and the light limiting effect of an infrared absorption layer is enhanced by enhancing the specific surface area of SOC, so that the light absorption is improved, and a high infrared absorption thermopile device is manufactured;
(4) the method for manufacturing the high-absorption composite structure thermopile provided by the invention is simple in process, is compatible with a CMOS (complementary metal oxide semiconductor) process and can improve the infrared absorption of a device.
Drawings
FIG. 1 is a schematic view of a structure formed in step 1 of example 1 of the present invention;
FIG. 2 is a schematic view of a structure formed in step 2 of example 1 of the present invention;
FIG. 3 is a schematic view of a structure formed in step 3 according to embodiment 1 of the present invention;
FIG. 4 is a schematic diagram of a thermopile structure according to example 1 of the present invention;
FIG. 5 is a schematic view of the structure formed in step 3 of example 2 of the present invention;
FIG. 6 is a schematic diagram of a thermopile structure in example 2 of the present invention.
In the above figures, the reference numerals have the following meanings:
1. a substrate; 11. a back cavity; 2. a support layer; 3. a polysilicon thermocouple; 4. a metal electrode; 5. a silicon nitride layer; 6. spin coating a carbon layer; 7. a nanopillar; 8. and (4) a nano-cone.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
As an aspect of the present invention, there is provided a thermopile including an infrared absorbing layer;
wherein, the infrared absorption layer comprises a spin-on carbon material.
In the embodiment of the invention, the infrared absorption layer comprises a spin-on carbon material, and the spin-on carbon has a light absorption effect and can enhance the light absorption effect of the infrared absorption layer.
In an embodiment of the invention, the thermopile comprises an infrared absorbing layer;
the infrared absorption layer is a composite lamination layer; the infrared absorbing layer includes:
a mid-infrared absorbing layer;
a near-infrared absorbing layer formed on the mid-infrared absorbing layer; wherein, the near-infrared absorption layer comprises a spin-on carbon material.
In a preferred embodiment of the present invention, a composite laminate is provided as the infrared absorbing layer, and the mid-infrared absorbing layer is combined with the near-infrared absorbing layer of spin-coated carbon material, so as to have a complementary absorption effect on light of different bands.
More specifically, when the mid-infrared absorption layer is made of silicon nitride, the absorption ratio of the mid-infrared absorption layer to light in a wave band of 7.6-11.6 microns is stronger; while SOC has a strong absorption ratio for light in the 1-5 μm wavelength band. The combination of the two increases the wavelength range of the absorbable light.
In an embodiment of the present invention, the infrared absorbing layer includes a plurality of nano-projections.
In an embodiment of the present invention, the nano-bump includes a nano-wire, a nano-pillar, or a nano-cone.
In the embodiment of the invention, the nano-protrusions can enhance the specific surface area of the infrared absorption layer and enhance the light limiting effect, namely the light capture. The nano-protrusions structurally improve light absorption, and a high infrared absorption thermopile is manufactured.
In an embodiment of the present invention, the material of the mid-infrared absorption layer includes silicon nitride, silicon carbide, or polysilicon material. More specifically, the mid-infrared absorption layer is made of a material compatible with CMOS.
In the embodiment of the invention, the thermopile sequentially comprises a thermocouple, a supporting layer and a substrate from top to bottom below the infrared absorption layer; wherein, the thermopile is also provided with a back cavity; the back cavity is formed by the substrate back release.
As another aspect of the present invention, there is also provided a method of manufacturing a thermopile, including: an infrared absorbing layer including a spin-on carbon material is formed by a spin-on method.
In an embodiment of the present invention, before forming the infrared absorption layer, the fabrication method further includes a step of epitaxially forming a support layer and a thermocouple on the substrate;
after the infrared absorption layer is formed, the manufacturing method further comprises the following steps:
step A: protecting the infrared absorption layer by using a protective film;
and B: etching on the substrate to form a back cavity;
and C: and removing the protective film by adopting an ashing process to finish the preparation.
More specifically, the protective film may be polyimide or photoresist. When the protective film is formed by spin coating of polyimide, the protective film is specifically formed by spin coating at a rotating speed of 1000-5000 rp/min and then baking and curing at a temperature of 120-250 ℃.
In an embodiment of the present invention, the preparing of the infrared absorption layer including a plurality of nano protrusions specifically includes: and etching the infrared absorption layer to form a plurality of nano bulges.
In the embodiment of the invention, the infrared absorption layer is etched by adopting a photoetching, electron beam photoetching or nano-imprinting method to form a plurality of nano-bulges;
before etching, the photoresist needs to use O2Trimming the plasma to form a preset nano convex shape;
during the etching process, the etching gas is O2The pressure is 1-20 mT, the upper RF power is 100-500W, and the lower RF power is 0-100W.
The technical solution of the present invention is further described below with reference to specific examples, but it should be noted that the following examples are only for illustrating the technical solution of the present invention, but the present invention is not limited thereto.
Example 1
The method for manufacturing the high-absorption composite structure thermopile in the embodiment 1 of the invention comprises the following steps:
step 1: depositing a support layer 2 and a thermocouple on a substrate 1 in sequence; and a silicon nitride layer 5 is deposited as a mid-infrared absorbing layer.
More specifically, as shown in fig. 1, a support layer 2, a polysilicon thermocouple 3, a silicon oxide film, a metal electrode 4 and a silicon nitride layer 5 are sequentially formed on a substrate 1 from bottom to top; the formation of the structure specifically comprises the following substeps:
substep 111: forming a support layer 2 on the front surface of a substrate 1;
the supporting layer 2 sequentially comprises a layer of silicon oxide, a layer of silicon nitride and another layer of silicon oxide from the front side of the substrate 1 to the top;
the deposition forming method of the support layer 2 includes a low pressure chemical vapor deposition method (LPCVD), a rapid thermal chemical vapor deposition method (RTCVD), or a plasma enhanced chemical vapor deposition method (PECVD);
substep 112: forming a polysilicon thermocouple 3 on the support layer 2;
in the embodiment of the present invention, the polysilicon thermocouple 3 is a pair of P-type polysilicon thermocouples.
Substep 113: forming a silicon oxide film on the exposed area of the support layer 2 and the polysilicon thermocouple 3;
the deposition forming method of the silicon oxide film includes a low pressure chemical vapor deposition method (LPCVD), a rapid thermal chemical vapor deposition method (RTCVD), or a plasma enhanced chemical vapor deposition method (PECVD);
substep 114: forming an electrode contact hole on the silicon oxide film, wherein the electrode contact hole extends to the surface of the polycrystalline silicon thermocouple 3;
in the embodiment of the invention, the electrode contact hole is formed by using a common photoetching method.
Substep 115: forming a metal electrode 4 on the silicon oxide film having the electrode contact hole;
in the embodiment of the present invention, the metal electrode 4 is made of aluminum.
The above is only an embodiment of the present invention, and the structure and the forming method of the thermocouple are not limited thereto, as long as the thermoelectric element and the manufacturing method capable of realizing the thermoelectric effect of the thermopile are applicable to the present invention.
Substep 116: forming a silicon nitride layer 5 on the silicon oxide film having the metal electrode 4; wherein, the silicon nitride layer 5 exposes the leading-out end region of the metal electrode 4.
In an embodiment of the present invention, the deposition method of the silicon nitride layer 5 includes a Low Pressure Chemical Vapor Deposition (LPCVD), a Rapid Thermal Chemical Vapor Deposition (RTCVD), or a Plasma Enhanced Chemical Vapor Deposition (PECVD).
Step 2: the deposition mode of the spin-coating carbon layer 6 is made by spin coating;
as shown in fig. 2, a spun-on carbon layer 6 is deposited as a near-infrared absorbing layer on the silicon nitride layer 5, forming an infrared absorbing layer of a composite laminate.
And step 3: and etching the infrared absorption layer to form the nano-pillars 7 with the array structure.
More specifically, the infrared absorption layer is etched by adopting a photoetching method to form a plurality of nano-columns 7;
before etching, the photoresist needs to use O2Trimming the plasma to form a preset nano-pillar shape;
during the etching process, the etching gas is O2The pressure is 1-20 mT, the upper RF power is 100-500W, and the lower RF power is 0-100W.
Resulting in SOC nanopillars 7 as shown in fig. 3.
And 4, step 4: carrying out a large-area deep silicon etching process on the back surface of the substrate 1 to manufacture a hollowed-out back cavity 11;
step 411: protecting the infrared absorption layer by using a protective film;
more specifically, the protective film is made of polyimide and is formed by spin coating, specifically, spin coating is carried out at the rotating speed of 1000-5000 rp/min, and then baking and curing are carried out at the temperature of 120-250 ℃.
Step 412: etching a substrate 1 to form a back cavity 11; the back cavity 11 with the back surface hollowed out is manufactured by adopting a dry process,
step 413: and removing the protective film by adopting an ashing process to finish the preparation, thus obtaining the thermopile structure shown in fig. 4.
Example 2
In embodiment 2 of the present invention, the manufacturing method is different from embodiment 1 in that step 3 is to etch the infrared absorption layer to form the nanopyramids 8 in the array structure as shown in fig. 5.
In the embodiment 2 of the present invention, the difference between the high absorption composite structure thermopile and the embodiment 1 is that the nano-protrusions of the infrared absorption layer of the thermopile in the embodiment 2 are nano-cones 8 as shown in fig. 6.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A thermopile, characterized in that said thermopile comprises an infrared absorbing layer;
wherein, the infrared absorption layer comprises a spin-on carbon material.
2. The thermopile of claim 1, comprising:
the infrared absorption layer is a composite lamination layer; the infrared absorbing layer includes:
a mid-infrared absorbing layer;
a near-infrared absorbing layer formed on the mid-infrared absorbing layer; wherein, the near-infrared absorption layer comprises a spin-on carbon material.
3. The thermopile of claim 1 or 2, wherein the infrared absorbing layer comprises a plurality of nano-bumps.
4. The thermopile of claim 3, wherein the nano-bumps comprise nanowires, nano-pillars, or nano-pyramids.
5. The thermopile of claim 2, wherein the mid-infrared absorbing layer comprises a silicon nitride, silicon carbide, or polysilicon material.
6. The thermopile of claim 1, further comprising a thermocouple, a support layer, and a substrate in that order from top to bottom below the infrared absorbing layer; wherein the thermopile is further provided with a back cavity; the back cavity is formed by releasing the back surface of the substrate.
7. A method for manufacturing a thermopile, comprising: an infrared absorbing layer including a spin-on carbon material is formed by a spin-on method.
8. The fabrication method according to claim 7, wherein before forming the infrared absorption layer, the fabrication method further comprises a step of epitaxially forming a support layer and a thermocouple on the substrate;
after the infrared absorption layer is formed, the manufacturing method further comprises the following steps:
step A: protecting the infrared absorption layer by using a protective film;
and B: etching the substrate to form a back cavity;
and C: and removing the protective film by adopting an ashing process to finish the preparation.
9. The method of claim 7, wherein the preparing the infrared absorbing layer including the plurality of nano-protrusions specifically includes: and etching the infrared absorption layer to form a plurality of nano bulges.
10. The method of making a thermopile of claim 9,
etching the infrared absorption layer by adopting a photoetching, electron beam photoetching or nano-imprinting method to form a plurality of nano-bulges;
before etching, the photoresist needs to use O2Trimming the plasma to form a preset nano convex shape;
during the etching process, the etching gas is O2The pressure is 1-20 mT, the upper RF power is 100-500W, and the lower RF power is 0-100W.
CN202010874367.1A 2020-08-26 2020-08-26 High-absorption thermopile and manufacturing method thereof Pending CN111969098A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112551479A (en) * 2020-12-08 2021-03-26 江苏创芯海微科技有限公司 High-performance MEMS infrared sensor and preparation method thereof

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CN1274078A (en) * 1999-03-24 2000-11-22 石塚电子株式会社 Thermal-stacking infrared sensor and mfg. method thereof
CN102329086A (en) * 2011-07-22 2012-01-25 北京金盛微纳科技有限公司 Method for producing film with high visible light absorption and high infrared radiation performances
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Publication number Priority date Publication date Assignee Title
JPH09288010A (en) * 1996-04-24 1997-11-04 Matsushita Electric Ind Co Ltd Pyroelectric infrared detecting element and its manufacture
CN1274078A (en) * 1999-03-24 2000-11-22 石塚电子株式会社 Thermal-stacking infrared sensor and mfg. method thereof
CN102329086A (en) * 2011-07-22 2012-01-25 北京金盛微纳科技有限公司 Method for producing film with high visible light absorption and high infrared radiation performances
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112551479A (en) * 2020-12-08 2021-03-26 江苏创芯海微科技有限公司 High-performance MEMS infrared sensor and preparation method thereof

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